Pyrophosphato titanate adducts

ABSTRACT

Adducts of tetrasubstituted pyrophosphato titanates and/or amines, having the formula XcTi[OP(O)(OR1)OP(O)(OR2)OR3)]4-c (NR4R5R6)d[P(OR7)(OR8)(OR9)]e,  are useful in improving the physical and chemical properties of many filled resins.

This is a division, of application Ser. No. 070,907, filed Aug. 29,1979, Pat. No. 4,277,415.

BACKGROUND OF THE INVENTION

The present invention relates to adducts of tetrasubstitutedpyrophosphato titanates with phosphites and/or amines. The pyrophosphatotitanate adducts of the present invention are useful in controlling theviscosity, flow and the conductivity of many filled resins. They improvethe physical and chemical properties of many filled resins therebypermitting more valuable and more stringent usage with maintained easeof processing. They also serve as acid catalysts in various applicationsand inhibit water/salt caused corrosion in treated substrates.

The titanates of the present invention differ from the pyrophosphatotitanates disclosed in U.S. Pat. Nos. 4,122,062 and 4,087,402 primarilyby the controlled reactivity of the titanates presently mentioned whichpermits long term storage of said titanates and of the treatedfiller/pigment resin at ambient to moderately elevated temperatures, anda very specific initiation of functional rates of activity to occur atcontrolled temperatures depending upon the specific adduct ligandemployed. Other advantages conferred upon pyrophosphato titanates byadduction as taught in the present invention include a substantiallyreduced tendency for such adducts to crystallize as compared to theirnon-adducted analogs thereby permitting greater ease of dispersion inmore vehicles and decreased acidity. In addition, many of thenitrogeneous adducts are water soluble, thereby permitting use ofaqueous vehicles in conjunction with fillers and pigments which wereheretofore incompatible in water as well as the incorporation of wateras a diluent in organic systems which were previously incapable ofaccepting significant water dilution.

SUMMARY OF THE INVENTION

The pyrophosphato titanate adducts of the present invention may berepresented by the following formula:

    X.sub.c Ti[OP(O)(OR.sup.1)OP(O)(OR.sup.2)(OR.sup.3)].sub.4-c -

    (NR.sup.4 R.sup.5 R.sup.6).sub.d [P(OR.sup.7)(OR.sup.8)(OR.sup.9)].sub.e I

In Formula I, c is 1 or 2; d is 0, 1 or 2; and e is 0, 1 or 2, with theproviso that d plus e must be 1 or 2. When c is 2, X is either RO-- or agroup which taken together with the Ti to which it is attached forms aring having the following Formula VI: ##STR1## when c is 1, however, Xmust be RO--. In Formula VI, each of f, g, h and i is 0 or 1, with theproviso that at least one of g, h and i is 1 and that the sum of f, g, hand i is 2 or 3. Each R is independently chosen from among 1 to 10carbon alkyl groups, 3 to 10 carbon alkenyl groups, 7 to 10 carbonaralkyl groups, 2 to 10 carbon oxyalkylene groups and 3 to 10 carbondioxyalkylene groups. R¹, R², R⁴, R⁷, each R¹⁰ and R¹¹ are independentlychosen from among hydrogen, 6 to 10 carbon aryl groups, 7 to 20 carbonaralkyl groups, 1 to 20 carbon alkyl groups, 3 to 20 carbon alkenylgroups, 2 to 20 carbon oxyalkylene groups and 3 to 20 carbonoligooxyalkylene groups, except that one and only one of R¹ and R² mustbe hydrogen. R⁵, R⁶, R⁸ and R⁹ are independently chosen from the samegroups as R¹, R², R⁴, R⁷, R¹⁰ and R¹¹ except that R⁵, R⁶, R⁸ and R⁹ maynot be hydrogen. R⁵ and R⁶ may also be independently chosen from among 1to 10 carbon alkyl, 3 to 10 carbon alkenyl, 6 to 10 carbon aryl and 7 to10 carbon aralkyl groups. These last four groups optionally have from 1to 3 carboxylate groups or from 1 to 3 carboxamide groups assubstituent. Each such substituent may be saturated or unsaturated andhave from 1 to 5 carbon atoms. R⁵ and R⁶ may also be independentlychosen from among 1 to 10 carbon alkanols, 2 to 6 carbon alkadiols or 7to 10 carbon aralkanols. When aromatic carbons are present in R, R², R⁴,R⁷, R¹⁰ and R¹¹ groups, each of said carbons is optionally substitutedby 1 or 2 independently selected halogen atoms (for example, fluorine,chlorine, bromine or iodine).

The present invention also relates to the use of such adducts fortreating particulate fillers, including pigments, the compositions offillers and the aforesaid adducts with thermoplastics, thermosets andcoating or casting resins, and the use of such adducts in conjunctionwith coating and casting resin compositions in the absence ofparticulates.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The aforementioned alkyl and alkenyl groups, and alkyl and alkyleneportions of the other aforementioned groups may be straight chain,branched chain or cyclic. Examples of alkyl groups are methyl, hexyl anddecyl. Examples of cyclic alkyl groups are cyclohexyl and cyclooctyl.Allyl and crotyl are examples of alkenyl groups. Oxyalkylene groups areexemplified by methoxymethyl and methoxyethyl. Aralkyl groups areexemplified by benzyl and beta naphthyl methyl. Examples of R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are likewise numerous. In additionto the above mentioned groups cited as examples of R, these groups arealso exemplified by higher carbon analogs of the above such asoctadecatrienyl and 2,4,6-trimethyl-1-cyclohexyl as well as by naphthyland biphenyl aralkyl groups such as 2-phenethyl, 2-chloro,4-bromophenylor naphthyl. In addition to the above, R⁵ and R⁶ are exemplified by suchgroups as 3-methacrylpropyl, and 2-acrylamidoethylhydroxy methyl anddihydroxy octyl.

The inorganic materials that may be treated with the titanate adducts ofthe present invention may be particulate or fibrous and of any shape orparticle size, the surfaces of which are reactive with the hydrolyzablegroup of the organo-titanium compound by means of hydroxyl groups, orabsorbed water, or both. Examples of such reactive inorganic materialsare the metal oxides of zinc, magnesium, lead, and calcium and aluminum,iron filings and turnings, and sulfur. Examples of inorganic materialsthat are reinforcing materials are metals, clay, carbon black, calciumcarbonate, barium sulfate, silica, mica, glass and asbestos. Examples ofsuch inorganic materials that are pigments are titanium dioxide, ironoxides, zinc chromate and ultramarine blue. As a practical matter, it ispreferable that the particle size of the inorganic material should notbe greater than 1 mm, preferably from 1 micron to 500 microns.

It is imperative that the titanate adduct be properly admixed with theinorganic material so as to permit the surface of the latter to reactsufficiently. The optimum amount of the titanate to be used is dependenton the effect to be achieved, the available surface area of and thebonded water in the inorganic material.

Reaction is facilitated by admixing under the proper conditions. Optimumresults depend on the properties of the titanate, namely, whether it isa liquid or solid, and its decomposition and flash point. The particlesize, the geometry of the particles, the specific gravity and thechemical composition, among other things, must be considered.Additionally, the treated inorganic material must be thoroughly admixedwith the polymeric medium. The appropriate mixing conditions depend onthe type of polymer, for example, whether it is thermoplastic orthermosetting, and its chemical structure, as will be readily understoodby those skilled in the art.

Where the inorganic material is pretreated with the titanate adduct, itmay be admixed in any convenient type of intensive mixer, such as aHenschel (trademark of Prodex) or Hobart (trademark of HobartCorporation) mixer or a Waring (trademark of Dynamics Corporation ofAmerica) blender. Even hand mixing may be employed. The optimum time andtemperature is determined so as to obtain substantial reaction betweenthe inorganic material and the organic titanate. Mixing is performedunder conditions at which the organic titanate is in the liquid phase,at temperatures below the decomposition temperature. While it isdesirable that the bulk of the hydrolyzable groups be reacted in thisstep, this is not essential where the materials are later admixed with apolymer, since substantial completion of the reaction may take place inthis latter mixing step.

Polymer processing, e.g., high shear mixing, is generally performed at atemperature well above the second order transition temperature of thepolymer, preferably at a temperature where the polymer will have a lowmelt viscosity. For example, low density polyethylene is best processedat a temperature range of 177° to 232° C.; high density polyethylenefrom 204° to 246° C.; and polystyrene from 232° to 260° C. Temperaturesfor mixing other polymers are known to those skilled in the art and maybe determined by reference to existing literature. A variety of mixingequipment may be used, e.g., two-roll mills, Banbury (trademark ofFarrel Corporation) mixers, double concentric screws, counter orcorotating twin screws and ZSK type of Werner and Pfleiderer (trademarkof Werner & Pfleiderer) and Bussex (trademark of Bussex Corp.) mixers.

When the titanate adduct and the inorganic materials are dryblended,thorough mixing and/or reaction is not readily achieved and the reactionmay be substantially completed when the treated filler is admixed withthe polymer. In this latter step, the titanate adduct may also reactwith the polymeric material if one or more of the groups on the titanateadduct is reactive with the polymer.

The ratio of pyrophosphato titanate to adducting agents is preferably1:1 or 1:2, with the latter ratio most preferred. Each adducting ligandmay be the same or different. In those formulations in which either thephosphorus based or the nitrogen based adducting agents are different,the product obtained is usually a mix of possible adducts includingmixed as well as identical ligands. In those adducts whereincombinations of nitrogen and phosphorus are employed, it is oftenpossible by control of stoichiometry and mode of addition to maintain analmost complete dispersity of product, if so desired.

When used in conjunction with particulates, the adducts of the presentinvention are employed at levels of at least 0.01 parts by weight,preferably from 0.1 to 5 parts by weight, and most preferably from 0.2to 2 parts by weight, per 100 parts by weight of inorganic solid. Theportion of adduct actually chosen by one skilled in the art is afunction of the inorganic solid, its surface area and the particulartitanium adduct selected. Upon reaction between the titanate and thesurface of the inorganic solid, the titanate becomes chemically bondedto at least a portion of the inorganic solid, thereby modifying thesurface considerably. The modified inorganic solid is generally far moreeasily dispersed in organic media than is the untreated solid. Fortreatment purposes, the titanate may be added to a suitable vehicle,such as water or a resin to be filled depending upon the investigator'sdesire and/or the nature of the titanate being employed. This additionis followed by appropriate shear to create an adequate level ofdispersion. The treated particulate, in addition to being moreeffectively coated, will almost certainly have substantially valuableadditional properties, such as the ability to act as a catalyst,improved adhesion to substrate, and/or the ability to activate across-linking agent in appropriate vehicle systems, primarily due to theavailability or organo-functionality added by attached titanatemolecules.

The amount of treated filler added to a resin generally ranges fromabout 1% to about 15% for a pigment and from about 1% to about 500% foran extender (all percentages are % by weight based on the weight of theresin). A wide variety of resins may be filled with fillers that aretreated with the titanate adducts of the present invention. Examples ofsuch resins are coating resins, casting resins, thermoplastic resins andthermosetting resins. Examples of all of the foregoing may be found inthe reference Modern Plastics Encyclopedia.

In many instances, it is advantageous to dilute the titanate with anappropriately compatible fluid before the titanate is introduced intoresin vehicles or before it is mixed with an inorganic particulate.Examples of appropriate inert fluids are aromatic hydrocarbons, ethersand glycol ethers. In many applications involving the use ofnitrogeneous adducts of pyrophosphato titanates, water may also beutilized as a solubilizing inert vehicle, particularly in applicationsinvolving subsequent use in aqueous systems, such as latex products.

The compounds of the present invention may be prepared by numerousroutes. Among the synthetic routes which have proven successful are theaddition of appropriate phosphites (Formula II) and/or amines (FormulaIII) to the corresponding pyrophosphato titanates (Formula IV) describedin U.S. Pat. No. 4,122,062 and U.S. Pat. No. 4,087,402. The reaction oftetraalkyl titanate phosphite adducts (Formula V), preparation of whichis described in U.S. Pat. No. 4,080,353 with addition of an appropriatepyrophosphate, an amine and/or a phosphite and/or a chelating agent mayalso be utilized, as may processes employing titanium tetrachloride inplace of tetraalkyl titanates. The aforementioned formulae are shownbelow: ##STR2## In Formulae II, III, IV and V, the various notations andfunctional groups have the definitions given above for Formula I.

Another synthetic route found useful for the preparation of thephosphite adducts of the present invention wherein the adduct ligandsare homogeneous is the reaction of tetraalkyl titanate with an admixtureof disubstituted pyrophosphoric acid and the phosphite ligand(s). Thislast technique is the preferred one for the preparation of mono and di-phosphite adducts of such pyrophosphato titanates. Variations of theaforementioned synthetic routes will be apparent to those skilled in theart.

The preparation of phosphite adducts of corresponding pyrophosphatotitanates may be accomplished under adiabatic conditions (since minimalheat evolution occurs) at any convenient temperature betweenapproximately -20° C. and approximately 150° C. The addition of thephosphite to the pyrophosphato titanate in either direct or reverseorder of addition will, in general produce minimal visual or thermalindication of reaction. However, typically a bathochromic shift of theabsorption maximum toward, and, occasionally even into the visualabsorption range, will generally be observed. Additionally, the meltingpoint will be depressed below that of the corresponding unadductedprecursor. Solubility of the resulting titanate in hydrocarbon mediawill generally be increased at the expense of the dispersibility inwater. By contrast, those adducts produced by the addition ofappropriately substituted amines to pyrophosphato titanates or theirphosphite adducts will generally provide substantial exotherms offormation together with displacement of stoichiometric proportions ofphosphite, if present, and will produce products of considerablyenhanced water solubility as compared to the parent pyrophosphatotitanate. Techniques employing the addition of dibasic pyrophosphates totetrasubstituted titanate adducts of phosphite and/or amines will alsogenerate substantial exotherms of formation and in both of these lattertwo synthetic approaches, temperatures should be kept within the rangeof approximately 0° C. to approximately 150° C. by external cooling inorder to minimize product degradation and/or by-product formation.Examples 1 through 4 below, are illustrative of the above mentionedtechniques in the order indicated above for the preparation ofpyrophosphato organo titanate adducts of the present invention.Subsequent examples 5 through 18 are illustrative of the utility of thematerials of the present invention for a variety of applications, suchas corrosion control, pigment/filler dispersion, catalyst activitycontrol and impact improvement. Preferred methods of incorporation ofthe titanate adducts of the present invention into filled resin systemsand their uses both in the presence and in the absence of fillers, forpurposes other that those listed above are also illustrated.

EXAMPLE 1 Preparation of Di(butyl,methyl) pyrophosphato ethylenetitanate di(dioctyl phosphite)

This example illustrates the sequential addition mode of phosphiteadduct formation.

206 g of dimethyl acid pyrophosphate (1 mole) and 296 g of dibutyl acidpyrophosphate (1 mole) were charged into a 2 liter stainless steel andglass assembly comprising a mechanically stirred 2 liter glass vesselequipped with a thermometer, addition funnel, and a water cooled jacket.285 g of tetraisopropyl titanate (1 mole) was added via the additionfunnel over a period of 1 hour. Cooling sufficient to prevent thereaction mass temperature from exceeding 150° C. was maintainedthroughout the addition period. After 20 minutes of further mixing, 62 gof ethylene glycol (1 mole) were added over a period of about 20minutes, at an addition rate and at a cooling rate such that thetemperature of the reaction mass was kept between 42° and 46° C. 612 gdioctyl phosphite (2 moles) were then added, all at once. The resultingmass was transferred to a 2 liter flask equipped for vacuum distillationand was distilled from a water bath to give a pot residue having aboiling point of 80° C. 231 g of isopropyl alcohol (3.85 moles, GLCassay greater than 98%) were recovered as a distillate via liquidnitrogen cooling of volatiles. Product recovery was 1246 g (100% yield).The product was a pale yellow low viscosity liquid which crystallizedslowly from a 40% solution in n-hexane at -20° C. to give light amberplatelike crystals having a melting point of 48°±3° C. Recovery was 1014g (81%). The omission of byproduct isopropanol removal lowered productrecovery on crystallization to 63%, but otherwise gave unchangedresults.

EXAMPLE 2 Preparation of Di(butyl, methyl) pyrophosphato ethylenetitanate di(dioctyl phosphite)

This example illustrates the preparation of the example adduct in situ.

The procedures, reaction conditions and materials exemplified in Example1 were employed except that the dioctylphosphite was introduced with thepyrophosphates prior to titanate addition. The nature of the crudeproduct produced and its yield (1248 g, 100%) were essentiallyunchanged, but this order of addition was found to provide severaloperating advantages. Among the advantages were lower and more uniformexotherms of tetraisopropyl titanate addition (possibly due to thelarger mass in the pot "heat sink," and/or to the more efficient coolingmade possible by the reaction mass' considerably lower viscosity) andvirtual freedom from the formation of crystalline intermediates ofundetermined nature which formed copiously during the procedure given inExample 1, unless the dispersion of tetraisopropyl titanate added wasextremely efficient.

It should be noted that other tetraalkyl titanates, e.g., methyl,n-butyl, t-butyl, or sec-octyl may be substituted for the tetraisopropyltitanate used in the illustration. However, the use of n-alkyl titanatesfrequently results in ligand exchange with the pyrophosphate moiety andmay therefore result in complex product mixtures, especially via theprocedure outlined in Example 1. Furthermore, the removal of higherboiling by-product alkanols, if desired, usually proved more difficultthan the removal of the more volatile lower alkanols. The removal ofby-product alcohol is optional and is not required for the preparationof the products of the present invention. Said removal merelyfacilitates product purification and/or may eliminate side reactions inalcohol sensitive substrates such as polyesters and urethanes and/or mayprovide decreased product flammability.

EXAMPLE 3 Preparation of Di(butyl,methyl) pyrophosphato, ethylenetitanate di(dioctyl phosphite)

Tetraisopropyl titanate di(dioctylphosphite), 901 g (1 mole), wascharged to a 2 liter stainless steel vessel equipped with an efficientagitator and external cooling. Temperature was maintained at or below45° C. during the sequential addition of 206 g (1 mole) of dimethyl acidpyrophosphate followed by 296 g (1 mole) of dibutyl acid pryophosphateover a period of approximately one hour each. Ethylene glycol 62 g (1mole) was then added. The reaction mixture was then transferred to aPyrex (trademark of Corning Glass for heat resistant borosilicate glass)glass system equipped for simple vacuum distillation and was distilledto give 1238 g (99% yield) of pale yellow oil having a boiling point ofgreater than 90° C. which slowly crystallized to produce a white waxycrystalline mass having a melting point of 49±4° C.

This procedure was not as satisfactory as that of Example 1, because itsuffered from the formation of localized gels during pyrophosphateaddition. These gels made mixing difficult.

EXAMPLE 4

Numerous examples of chelated pyrophosphato titanate adducts preparedvia the procedure given in Examples 1 to 3 are given in Table 1. Eachtitanate adduct is identified by a symbol in the extreme left handcolumn that similarly identifies the adduct in the Examples that follow.

                                      TABLE 1                                     __________________________________________________________________________                         Method of                                                                           Melting                                                                              Calculated                                  Pyrophosphato Titanate Adduct                                                                      Preparation                                                                         Point °C.                                                                     % P/Found % P                               __________________________________________________________________________    (A) ethylene di(butyl, octyl)pyro-                                                                 1,2,3 <0     16.4/16.1                                       phosphato titanate di(tris-                                                   ethylphosphite)                                                           (B) 1-oxo-1,3-propylene di(bis-                                                                    2,3   42 ± 5                                                                            15.0/14.8                                       phenyl)pyrophosphato titanate                                                 dilaurylphosphite                                                         (C) 1-oxo-2-phenylethylene, di(2-                                                                  1,2,3 54 ± 3                                                                            11.3/11.2                                       chloro-p-cresyl, methyl)pyro-                                                 phosphato titanate, triphenyl                                                 phosphite                                                                 (D) neopentenyl, di(bisoctadecyl)                                                                  1,3   27 ± 6                                                                            9.74/9.5                                        pyrophsphato titanate di(butyl,                                               propyl phosphite)                                                         (E) 1,3 propylene, di(bisoctadecyl)                                                                1     <0     9.26/9.3                                        pyrophosphato titanate di(di-                                                 benzyl phosphite)                                                         (F) oxoethylene di(butyl, methoxy-                                                                 1,2   <0     9.46/9.3                                        ethoxyethyl) pyrophosphato                                                    titanate dimethoxethylphosphite                                           (G) ethylene di(methyl, 11, 14-hexa-                                                               1,2,3 34 ± 6                                                                            16.2/16.1                                       decadienyl) pyrophosphato                                                     titanate di(bismethyl phosphite)                                          (H) 1,2-propenyl, di bis(2-bromo-3-                                                                1,3   64 ± 2                                                                            12.5/12.6                                       chloro-4-t-butylphenyl) pyro-                                                 phosphato titanate di(bishexa-                                                decyl phosphite)                                                          (I) ethylene di(butyl, methyl) pyro-                                                               1,2,3 73 ± 4                                                                            16.9/16.8                                       phosphato titanate di(tris-                                                   ethylamine)                                                               (J) oxoethylene di(butyl, octyl)                                                                   1     42 ± 5                                                                            13.3/12.9                                       pyrophosphato titanate 2-di-                                                  methylaminoisobutanol                                                     (K) ethylene di(bisoctyl)pyrophos-                                                                 1,3   82 ± 4                                                                            9.65/9.9                                        phato titanate di(3-dimethyl-                                                 aminopropylmethacrylamide                                                 (L) benzylethylene di(phenyl, lauryl)                                                              1     76 ± 4                                                                            9.57/9.7                                        pyrophosphato titanate di(ethyl-                                              aminoethyl acrylate                                                       (M) ethylene, di(butyl, methyl) pyro-                                                              1     not isolated*                                          phosphato titanate di(bisoctyl)                                               phosphite                                                                 (N) oxoethylene di(butyl, octyl)pyro-                                                              1     not isolated*                                          phosphato titanate diphenyl phos-                                             phite                                                                     (O) 2-methyl-2,4-butenyl di(di-p-                                                                  1     not isolated*                                          chlorobenzyl)pyrophosphato                                                    titanate di(butoxyethyl, methyl                                               phosphite                                                                 (P) oxoethylene, di(benzyl, 2-                                                                     1,2   not isolated*                                          pentenyl)pyrophosphato titanate                                               di(2-dimethylamino) isobutanol                                            (Q) 2,3-butenyl di(bis-4-methoxy-                                                                  1     not isolated*                                          phenyl)pyrophosphato titanate                                                 diethylamine                                                              (R) 2,3-dimethyl-2,3-butenyl di(bis-                                                               1     not isolated*                                          methyl)pyrophosphato titanate                                                 triethylamine, dibutyl phosphite                                          (S) oxoethylene di(p-bromobenzyl)                                                                  1     not isolated*                                          pyrophosphato titanate methyl-                                                aminoethanol                                                              (T) 1-oxoprop-1,3-enyl di(butoxy-                                                                  1     not isolated*                                          methoxyethyl, isobutyl)pyro-                                                  phosphato titanate di(bistridecyl)                                            phosphite                                                                 (U) methoxyethylene di(bispropyl)                                                                  1     not isolated*                                          pyrophosphato titanate di                                                     propylamino ethyl methacrylate                                            (V) isopropyl, tri(butyl, methyl)                                                                  1,2,3 <0     17.0/16.8                                       pyrophosphato titanate di(bis-                                                octyl phosphite)                                                          (W) isopropyl, tri(bisoctyl)pyro-                                                                  1,2,  16 ± 5                                                                            12.9/12.8                                       phosphato titanate triethanol-                                                amine                                                                     (X) isooctyl, tri(bismethyl)pyro-                                                                  1,2,3 not isolated*                                          phosphato titanate tripropyl                                                  phosphite                                                                 (Y) ethoxytriglycolyl, tri(4-bromo-                                                                1     14 ± 6                                                                            15.3/15.1                                       phenyl, methyl)pyrophosphato                                                  titanate di(methoxyethyl)                                                     phosphite                                                                 (Z) 4-ethoxybenzyl tri(di-alphanaph-                                                               1     64 ± 5                                                                            10.4/10.1                                       thyl) pyrophosphato titanate di                                               (di-ethylaminoethyl(methacrylate)                                         (AA)                                                                              t-butyl, tri(bisbutyl) pyro-                                                                   1     12 ± 4                                                                            17.2/17.0                                       phosphato titanate tri-methyl                                                 phosphite, dimethylaminoethanol                                           (AB)                                                                              methyl, tri(bis-4-chlorophenyl)                                                                1     48 ± 3                                                                            15.8/15.5                                       pyrophosphato titanate dioctyl                                                phosphite, dimethylaminoethyl                                                 formamide                                                                 (AC)                                                                              allyl, tri(allyl, methyl)pyro-                                                                 1,3   23 ± 3                                                                            20.2/19.9                                       phosphato titanate trimethyl                                                  phosphite, dioctyl phosphite                                              (AD)                                                                              (2,2-diallyloxymethyl)ethyl                                                                    1,2   38 ± 4                                                                            11.9/11.7                                       tri(bisbutyl)pyrophosphato                                                    titanate di(trisphenyl phosphite)                                         (AE)                                                                              1-(2-butenyl)tri(methyl, octyl)                                                                1     31 ± 3                                                                            13.1/12.9                                       pyrophosphato titanate, tri-                                                  ethylamine, dioctyl phosphite                                             __________________________________________________________________________     *by-product alcohol not removed, reaction mixture used as such.          

EXAMPLE 5

This example illustrates the utility of various titanate adducts of thepresent invention as corrosion retardants.

Xylene degreased 20 mil panels of cold rolled steel were dip coated witha 1 weight percent solution of additive in toluene followed by a toluenewash and were then oven dried at 150° C. in a nitrogen atmosphere. Thedried panels were cooled, weighed, subjected to 100 hours of 100%humidity at 40° C. exposure in an environmental cabinet, re-dried,cooled, and re-weighed. The corrosion rate in mils per year wascalculated from the following equation: ##EQU1## The results of a studyof selected examples of the titanates of the present invention are givenin Table 2.

                  TABLE 2                                                         ______________________________________                                                     Indicated Corrosion                                              Adduct       Rate (mils/yr) % of Control                                      ______________________________________                                        None (control)                                                                             172            100                                               A            38             22                                                B            26             15                                                C            69             40                                                D            81             47                                                E            24             14                                                F            13             8                                                 G            32             19                                                H            19             11                                                I            20             12                                                J            31             18                                                K            38             22                                                L            35             20                                                X            17             10                                                Y            20             12                                                AB           26             15                                                AC           18             10                                                AD           41             24                                                AE           38             22                                                ______________________________________                                    

In each instance, the materials of the present invention improvedhumidity resistance of cold rolled steel by at least two-fold and in thecase of the F material, the improvement was twelve-fold.

EXAMPLE 6

Titanate adducts M through U, identified above, were compounded into analkyl-melamine baking enamel having a brown color as indicated below.The resultant formulations were each oven baked at 100° C. for a periodadequate to provide a film pencil hardness (Society of CoatingsTechnology Test) of F-H at 1.3±0.2 mils dry film thickness. The resultsof this study are given in Table 3.

The following materials were premixed, on a high shear disperser, atambient temperature for fifteen minutes:

    ______________________________________                                        Material             Kilograms  Liters                                        ______________________________________                                        soya alkyd short oil,                                                                              172        174                                           Cook #S-157-A-2 (trademark of                                                 Cook Paint and Varnish Co.)                                                   pyrophosphato titanate adduct                                                                      0.397      0.33                                          titanium dioxide, DuPont #R-960                                                                    21         5.08                                          (trademark of E.I. DuPont                                                     de Nemours, Co.)                                                              magnesium silicate   32         12.0                                          lamp black           0.9        0.512                                         red iron oxide       3.2        0.648                                         yellow iron oxide    15         3.72                                          bentonite clay       1.1        0.633                                         fumed silica         1.1        0.523                                         soya lecithin        1.4        1.42                                          ______________________________________                                    

Tetraoctyltitanate di(dioctyl)phosphite (0.188 kilograms, 0.20 liters)was added to the above mixture and the mixture was further mixed on asand mill until the particle size was Hegman 6.5 grind guage. Theresulting blend was added to the following Material Letdown Solution andwas mixed at ambient temperature.

    ______________________________________                                        Material Letdown Solution                                                                          Kilograms  Liters                                        ______________________________________                                        xylene               41.8       48.5                                          Butyl Cellosolve (trademark of Union                                                               10.2       11                                            Carbide Corporation)                                                          triethylamine        2.0        2.73                                          n-butanol            0.90       1.12                                          50% melamine formaldehyde resin,                                                                   74.5       76                                            Cargil #2218 (trademark of                                                    Cargill Inc.)                                                                 6% Cobalt naphthenate                                                                              0.90       0.95                                          ______________________________________                                    

The resulting paint composition had the following properties:

    ______________________________________                                        weight per liter        1.05                                                  viscosity (#2 Zahn ± 6 sec.)                                                                       28.0                                                  volume solids (%)       32.0                                                  weight solids (%)       49.0                                                  thickness dry film      1.0-1.75                                              pencil hardness         F-H                                                   gloss (±5°)   55.0                                                  letdown solution to grind ratio                                                                       5:1                                                   ______________________________________                                    

The bake time at 93° C. required to achieve specification hardness wasdetermined for several titanate adducts of the present invention. Theresults are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                                           Bake Time at 93° C.                                                    Time required to                                           Pyrophosphato Titanate                                                                           achieve specification                                      Adduct Employed    hardness (+2 minutes)                                      ______________________________________                                        None (control)     117                                                        M                  43                                                         N                  41                                                         O                  57                                                         P                  84                                                         F                  21                                                         Q                  39                                                         R                  48                                                         S                  83                                                         T                  42                                                         U                  38                                                         ______________________________________                                    

The reduction in bake time required in order to achieve specificationproperties is clearly shown to be substantial for all members of theclass tested. A considerable reduction in cost results from the savingsin both time and energy expended during baking.

EXAMPLE 7

This example illustrates the utility of certain pyrophosphato titanateadducts in the simultaneous control of viscosity and pot life ofpolyester casting resins.

Polyester resin composites were prepared by thoroughly admixing in thefollowing order, 100 g of polyester resin (#30001, trademark ofReichhold Chemical Co.), 0.5 g of pyrophosphato titanate adduct, 100 gof talc (#42, trademark of Englehard Mineral & Chemical Co.), and 1 g of6% cobalt naphthenate. The resultant dispersions were deaerated bymixing in vacuo to eliminate variable air entrainment. The viscositiesof the dispersions were then measured employing a Brookfield RVFviscosimeter (trademark of Brookfield Corp., Stoughton, Mass.).Thereafter, 0.5 g of methyl ethyl ketone peroxide was added to 100 galiquots of deaerated dispersion and pot life was measured (time toachieve 2 million cps viscosity) at 21° C. The results are given inTable 4.

                  TABLE 4                                                         ______________________________________                                                     Viscosity of Composite                                           Adduct Employed                                                                            (thousands of poise)                                                                            Minutes                                        ______________________________________                                        None         2.7               33                                             N            1.6               109                                            O            1.3               127                                            F            0.8               18                                             T            1.4               142                                            U            0.6               14                                             V            3.7               37                                             W            5.2               35                                             ______________________________________                                    

The data show that the phosphite adducts N, O and T retard the increaseof viscosity due to premature gellation, thereby providing substantiallyincreased useful working pot life, whereas the unsaturated nitrogenbased adducts F and U act as accelerators, useful where rapid cure isdesired. Furthermore, all of the adducts tested, other than V and W,provided the bonus of lower composite viscosities useful in many lowenergy application situations. Adducts V and W acted as thixotropeswithout material effect on pot life, a characteristic not shared byconventional thixotropes such as fumed silica and asbestos which,normally, markedly slow peroxide cures.

EXAMPLE 8

This example illustrates the use of various pyrophosphato titanateadducts to improve the scrubbability of a latex coating.

Test batches of latex paint were prepared by mixing 25 g of titaniumdioxide (DuPont #R931, trademark of E. I. DuPont de Nemours) in 20 g ofethylene glycol monobutyl ether containing 0.25 g of pyrophosphatotitanate adduct on a high shear disperser (at constant torque) to aHegman grind gauge of minus 6. This was followed by letdown (dilution)with 100 g of acrylic latex (Ucar 4550, trademark of Union CarbideCorp.). Test panels were then prepared as 3 mil wet (about 2 mil dry)drawdowns on toluene degreased mild steel and the resultant films weredried at 25° C. for 48 hours prior to scrub testing. The scrub testeremployed was a 1/8" wide, 10 micron silica impregnated phenolic grindingwheel rotated at 10 RPM. Grinding was continued in each case untilmagnetic dust was detected. Results are given in Table 5.

                  TABLE 5                                                         ______________________________________                                                  Grind Time (minutes)                                                Adduct    Required for -6(Hegman)                                                                         Scrub Cycles                                      ______________________________________                                        Control   22                38                                                B         14                57                                                C         12                83                                                D         13                71                                                E         9                 46                                                Q         14                143                                               G         15                71                                                H         12                62                                                I         14                49                                                J         13                53                                                K         15                168                                               ______________________________________                                    

These data show that the use of the adducts of the present inventionmarkedly improved both the grinding efficacy and the scrub resistance inthose formulations in which they were employed and that in several cases(C, F and K) the improvements in scrub resistance were twofold orhigher.

EXAMPLE 9

This example illustrates the utility of pyrophosphato titanium adductsof the present invention for the improvement of epoxy polyamidecoatings.

The coating components A and B were prepared separately by mixing theingredients listed in Tables 6A and 6B, respectively, in the orderindicated at 33° C. to 45° C., using a Cowles dissolver (trademark ofMoorhouse Cowles Co.). Components A and B were admixed at ambienttemperature using the same equipment. Q-panels (trademark of Q-PanelCorp.) of cold rolled steel were coated with portions of the testcoating to provide a film one mil dry thickness. The coatings were agedfor one week at ambient temperature before testing. Test results aregiven in Table 6C.

                  TABLE 6A                                                        ______________________________________                                        Component A                                                                                    BLSC Control                                                                              Silica System                                    Ingredient       Parts by weight                                                                           Parts by weight                                  ______________________________________                                        epoxy resin (Araldite                                                                          210         210                                              571CX80, trademark                                                            of Ciba-Geigy Corp.)                                                          basic lead silicochromate                                                                      480         None                                             (BLSC)                                                                        titanium dioxide 30          30                                               red iron oxide   15          15                                               fumed silica     6.4         6.4                                              talc             235         235                                              amorphous silica None        400                                              xylene           193         193                                              diacetone alcohol                                                                              96          96                                               urea formaldehyde resin                                                                        10.5        10.5                                             (Beetle 216-8, trademark                                                      of America Cyanamid Corp.)                                                    chelated pyrophosphato                                                                         None        3.3                                              titanate adduct                                                               parts by weight  1276        1199                                             ______________________________________                                    

                  TABLE 6B                                                        ______________________________________                                        Component B                                                                                  BLSC Control Silica System                                     Ingredient     Parts by weight                                                                            Parts by weight                                   ______________________________________                                        polyamide curative                                                                           105          105                                               (Araldite 820, trademark                                                      of Ciba-Geigy Corp.)                                                          xylene         24           24                                                butanol        12           12                                                parts by weight                                                                              141          141                                               ______________________________________                                    

The cost per gallon of the Component A BLSC Control was $1.35; the costper gallon of the Component A titanate adduct formulation was about$0.66.

                  TABLE 6C                                                        ______________________________________                                                                   Rusting  Stripped                                                             after 1000                                                                             panel rust-                                                          hour salt                                                                              ing after                                        Initial  Four Month fog expo-                                                                              500 hours,                                       viscosity                                                                              viscosity  sure at  100% humid-                               Adduct KU*      KU         27° C.                                                                          ity at 27° C.                      ______________________________________                                        BLSC                                                                          (Control)                                                                            192      216        M (moderate)                                                                           S (severe)                                B      112      126        Sl (slight)                                                                            Sl                                        C      103      104        Sl       M                                         D      106      118        Sl       Sl                                        E      102      104        Sl       Sl                                        Q      116      109        Sl       M                                         G      109      111        M        M                                         H      113      115        Sl       Sl                                        I       96      100        M        Sl                                        J      101      107        Sl       Sl                                        ______________________________________                                         *Krebs units                                                             

Note that as compared with the BLSC Control, each of the pyrophosphatotitanate adducts of the present invention provided improved protectionagainst corrosion at a cost considerably lower than that of the BLSCControl without the employment of environmentally damaging heavy metalsas required by the best previously available technology. Alsodemonstrated are the massive viscosity reduction achieved via the use ofthe products of the present invention as a major contributing capabilityto the functional utility of the silica system since control viscositywould otherwise prevent effective application coverage.

EXAMPLE 10

This example illustrates the utility of pyrophosphato titanium adductsof the present invention as adhesion promoters for polymer laminates.

The titanate adducts listed in Table 7 below were compounded into virginlow density polyethylene (LDPE). Thirty mil sheets of the LDPE wereextrusion laminated onto preformed 50 mil Surlin (trademark of DuPont deNemours for metalated polyolefin) ionomer sheets at 107° C., employing a24:1 vented National Plastics Machinery (trademark) extruder. The peelstrength of each laminate was measured with a constant speed motor and astrain gauge at 27° C. after 24 hours at ambient temperature andpressure. The results PG,23 are given below in Table 7. The formulationscontained 0.2 weight percent of the indicated chelated pyrophosphatotitanium adduct on LDPE.

                  TABLE 7                                                         ______________________________________                                        Adduct      Peel Strength, kg/cm.sup.2                                        ______________________________________                                        Control     4.8                                                               A           9.0                                                               B           19                                                                C           20                                                                D           17                                                                E           20                                                                G           17                                                                H           16                                                                I           24                                                                Z           13                                                                ______________________________________                                    

Note that in each instance, the use of the adducts improved peelstrength (bonding) between the dissimilar polymer layers.

EXAMPLE 11

This example illustrates the utility of pyrophosphato titanium adductsof the present invention in enhancing the tensile and elongationproperties of cellulosics (cross-linked low density polyethylene filledwith cotton linters).

One hundred parts by weight of low density cross-linkable polyethylene,20 parts cotton linters (chopped to 20-45 micron length, 0.5 partsdicumyl peroxide and 0.2 parts of pyrophosphato titanate adduct werecompounded on a two roll mill at 93°±6° C. (all parts given are parts byweight). Samples were then press cured at 149° C. for 20 minutes. Thesamples were equilibrated at 21° C. for 24 hours prior to testing on anInstron (trademark of Instron Corporation) tensile tester at anextention rate of 0.2 inches/min. The results are given below in Table8.

                  TABLE 8                                                         ______________________________________                                        Adduct  Tensile Strength, kg/cm.sup.2                                                                  Elongation at Break, %                               ______________________________________                                        Control 6.11 × 10.sup.3                                                                          80                                                   A       6.53 × 10.sup.3                                                                          90                                                   D       7.95 × 10.sup.3                                                                          170                                                  Q       10.9 × 10.sup.3                                                                          230                                                  K       8.80 × 10.sup.3                                                                          210                                                  ______________________________________                                    

EXAMPLE 12

This example illustrates the use of pyrophosphato titanate adducts asviscosity control agents and/or dispersants in dissimilar media (forexample, water and mineral oil).

In each instance, the indicated titanate was precoated at 0.5 weightpercent on HiSil 223 (trademark of PPG Industries) in a household typeblender prior to dispersion in the liquid vehicle (water or mineral oil)at 70 weight percent HiSil using a Hochmeyer disperser (trademark ofHochmeyer Corp.). The resulting dispersions were evaluated at 27° C.using a Brookfield RVF viscometer (trademark). The results are given inTable 9.

                  TABLE 9                                                         ______________________________________                                               Aqueous dispersion visco-                                                                       Mineral Oil dispersion                               Additive                                                                             sity MCPS (10.sup.3 centipoise)                                                                 viscosity MCPS                                       ______________________________________                                        Control                                                                              152               23                                                   A      130               28                                                   B      37                56                                                   C      52                72                                                   D      168               22                                                   E      182               18                                                   Q      154               21                                                   G      172               19                                                   H      41                62                                                   I      227               separates rapidly                                    J      47                62                                                   K      164               18                                                   Z      194               17                                                   Y      184               18                                                   AD     171                                                                    ______________________________________                                    

This example demonstrates the wide range of viscosity control availablein vehicles as diverse as water and mineral oil via the employment ofsmall proportions of pyrophosphato titanium adducts in conjunction witha single (silica) particulate.

EXAMPLE 13

This example illustrates the utility of pyrophosphato titanium adductsas promoters of conductivity in metal filled polymer composites. In eachinstance, the metal indicated was precoated with the specified adduct byadmixture in a household type blender prior to incorporation into thepolymer base on a laboratory two roll mill. The formulations were presscured and formed as 6 inch×6 inch×100 mil sheets for 20 minutes at 170°C. and stress relieved at 27° C. for 24 hours, prior to evaluation.Resistivities were measured using a field effect transistor type ohmeterequipped with a decade runup box of 10¹ to 10⁹ ohms range on a throughthe sample basis. The results are given in Table 10 (Tables 10a, 10b and10c).

    ______________________________________                                                    Resistance     Resistance                                         Adduct      ohm/cm Nickel  ohm/cm Tin                                         ______________________________________                                        Control     1.3 × 10.sup.6                                                                         3.9 × 10.sup.6                               B           16             6.2 × 10.sup.2                               C           28             4.8 × 10.sup.2                               Q           45             87                                                 E           63             1.1 × 10.sup.2                               K           1.1 × 10.sup.2                                                                         96                                                 ______________________________________                                    

    ______________________________________                                        Adducts          Resistance ohm/cm                                            ______________________________________                                        Control          1.6 × 10.sup.8                                         B                2.0 × 10.sup.4                                         C                1.4 × 10.sup.4                                         E                4.7 × 10.sup.2                                         Q                6   × 10.sup.2                                         K                1.7 × 10.sup.2                                         Y                5.7 × 10.sup.5                                         Z                6.2 × 10.sup.3                                         AA               4.1 × 10.sup.3                                         AB               8.1 × 10.sup.1                                         AD               6.2 × 10.sup.2                                         AE               3.8 × 10.sup.2                                         ______________________________________                                    

                  TABLE 10c                                                       ______________________________________                                        Formulation (in parts by weight): Viton E430 (trademark of E.I.               duPont de Nemours for fluoroelastomer), 24; calcium hydroxide                 powder, regent grade (manufactured by J.T. Baker Chemical                     Company), 1.28; nickel (1 micron nominal powder), 75; pyrophos-               phato titanium adduct, 0.25.                                                  Adduct            Resistance ohm/cm                                           ______________________________________                                        Control           9 × 10.sup.8                                          B                 5 × 10.sup.5                                          C                 7 × 10.sup.4                                          E                 1.8 × 10.sup.2                                        Q                 38                                                          K                 61                                                          F                 6.1 × 10.sup.6                                        M                 5 × 10.sup.3                                          P                 8 × 10.sup.3                                          AB                3.4 × 10.sup.2                                        ______________________________________                                    

In each and every instance the use of pyrophosphato titanate adductprovided for substantial conductivity enhancement versus the control,despite the gross variation in polymer binders employed; (i.e. thesilicone and Viton (trademark) are grossly differing thermosets, and thePVC is a thermoplastic).

EXAMPLE 14

This example illustrates the use of selected pyrophosphato titaniumadducts as insulation value enhancers in hard clay filled flexiblepolyvinyl chloride.

SP-33 Clay (trademark of Burgess Pigment Co.), 20 parts by weight;dioctyl phthalate, 50; and pyrophosphato titanium adduct, 0.01; wereadmixed in a household type blender. The resulting mixture was added topolyvinyl chloride resin (Geon 103EP, trademark of B. F. Goodrich Co.),100; epoxidized soybean oil, 3; powdered lead diphthalate, 3; andstearic acid, 0.3, all quantities are in parts by weight. The mix wascompounded on a laboratory two-roll mill at 135° C. and press-formed for10 minutes at 160° C. prior to evaluation of resistance of a sheethaving a cross-section of about 100 mils by employing a mehohm Bridgecoupled to a 10⁴ -10⁵ ohm decade box assembly. The results are shown inTable 11.

                  TABLE 11                                                        ______________________________________                                        Adduct      Resistance ohms/cm                                                ______________________________________                                        Control     5 × 10.sup.12                                               B           2 × 10.sup.13                                               C           3 × 10.sup.13                                               D           8 × 10.sup.12                                               Q           7 × 10.sup.12                                               J           1 × 10.sup.13                                               ______________________________________                                    

These data show that significant resistivity increases result from theemployment of pyrophosphato titanate adducts in vinyl based insulation.

EXAMPLE 15

This example illustrates the advantages in terms of shelf stabilityresulting from the adduction of pyrophosphato titanates with certaintypes of amines and/or phosphites.

Test formulations containing 40 weight percent Bakelite CK-1634 phenolicresin (trademark of Union Carbide Corp.) and 10 weight percent ofpowdered coal (Carbofil #1--Shamokin Filler Co.), together with 0.2weight percent of pyrophosphato titanate (as shown) in xylene werecoated on aluminum Q-pannels (trademark of Q-Pannel Corp.) to a wet filmthickness of 5 mils and placed in a 150° C. forced draft oven until theresultant film showed a pencil hardness of 3H. A second sample of eachformulation was shef aged in a closed container, at 25°±3° C. todetermine package stability. The test results are shown in Table 12.

                  TABLE 12                                                        ______________________________________                                        Pryophosphato Titanate                                                                      Shelf Life (days).sup.(1)                                                                   Cure Time Min.                                    ______________________________________                                        Control (none)                                                                              60 ± 3     25 ± 3                                         A             55 ± 5     16 ± 2                                         non-adducted A.sup.(2)                                                                      22 ± 2     15 ± 2                                         B             >120          14 ± 2                                         non-adducted B                                                                              20 ± 3     15 ± 2                                         J             >120          17 ± 2                                         non-adducted J                                                                              20 ± 3     16 ± 2                                         (same as A)                                                                   K             >120          20 ± 2                                         non-adducted K                                                                              28 ± 3     19 ± 2                                         Q             >120          16 ± 2                                         non-adducted Q                                                                              22 ± 3     15 ± 2                                         (same as A)                                                                   AA            74 ± 5     11 ± 2                                         non-adducted AA                                                                             18 ± 3     10 ± 2                                         AE            82 ± 5     12 ± 2                                         non-adducted AE                                                                             16 ± 4     12 ± 2                                         ______________________________________                                         .sup.(1) Time to 100% Brookfield (trademark) viscosity increase               .sup.(2) Prepared as disclosed in U.S. Pat. No. 4,122,062 or 4,087,402   

This example shows that while both adducted and non-adductedpyrophosphato titanates decrease cure time with consequent reduction inenergy requirements when employed in conjunction with phenolic resins,the non-adducted analogs negatively effect formulation shelf lifewhereas their adducted analogs either effect shelf life positively ornegligibly compared to the control. This example also shows that thechoice of adducting agent also has a substantial effect on theproperties of the resulting adduct.

EXAMPLE 16

This example shows the advantages of appropriate adduction ofpyrophosphato titanates for purposes of melting point depression andease of dispersion. One gram of the specified adducts of the presentinvention and, separately, their non-adducted analogs were added toseparate 200 mil portions of water. 100 grams of Optiwhite Calcined Clay(trademark of Burgess Corp.) was then dispersed at 30°±5° C. using aHochmeyer disperser and the viscosity of each dispersion measuredimmediately and after boiling for two hours at 30°±1° C. using aBrookfield RVF viscometer (trademark of Brookfield Corp.). The resultsare shown in Table 13.

                  TABLE 13                                                        ______________________________________                                        Pyrophosphato                                                                              Initial 30° C.                                                                      Boiled dispersion                                   Titanate Employed                                                                          viscosity (cps)                                                                            30° C. viscosity (cps)                       ______________________________________                                        Control      4.3 × 10.sup.5                                                                       >10.sup.7                                           I            6.7 × 10.sup.3                                                                       >10.sup.7                                           non-adducted I                                                                             4.1 × 10.sup.5                                                                       >10.sup.7                                           J            3.9 × 10.sup.3                                                                       5.2 × 10.sup.4                                non-adducted J                                                                             4.5 × 10.sup.5                                                                       >10.sup.7                                           K            6.3 × 10.sup.4                                                                       4.7 × 10.sup.4                                non-adducted K                                                                             5.0 × 10.sup.5                                                                       >10.sup.7                                           L            3.9 × 10.sup.3                                                                       8.4 × 10.sup.3                                non-adducted L                                                                             4.0 × 10.sup.5                                                                       >10.sup.7                                           W            6.1 × 10.sup.3                                                                       >10.sup.7                                           non-adducted W                                                                             4.2 × 10.sup.5                                                                       >10.sup.7                                           Z            4.8 × 10.sup.5                                                                       5.2 × 10.sup.5                                non-adducted Z                                                                             4.5 × 10.sup.5                                                                       >10.sup.7                                           AB           2.9 × 10.sup.2                                                                       >10.sup.7                                           non-adducted AB                                                                            4.5 × 10.sup.5                                                                       >10.sup.7                                           AE           8.2 × 10.sup.4                                                                       9.5 × 10.sup.5                                non-adducted AE                                                                            4.1 × 10.sup.5                                                                       >10.sup.7                                           ______________________________________                                    

This example shows that pyrophosphato titanate adducts of the presentinvention may be utilized to achieve controlled viscosity reduction ofaqueous clay dispersions at ambient temperature with or withoutcontrolled viscosity lowering after boiling whereas their non-adductedanalogs give essentially negligible response in comparable formulations.

EXAMPLE 17

This example shows the utility of adduction of pyrophosphato titanateswith amines of Formula III and/or phosphites of Formula II with respectto melting point reduction and with respect to solubility enhancement inselected media.

The indicated phosphato titanates, prepared according to the proceduresdescribed in U.S. Pat. Nos. 4,122,062 or 4,087,402, were converted tothe indicated adducts via the procedure outlined in Example 1 andsolubility (as weight percent) at 25°±3° C. was measured in n-hexane(Hexane sol.). Melting points of the phosphato titanate were determinedbefore and after adduction. The results are given in Table 14.

                  TABLE 14                                                        ______________________________________                                        Pyrosphos-                Pyrophos-                                           phato non-       Hexane   phato          Hexane                               adducted                                                                              Melting  sol.     Titanate                                                                              Melting                                                                              sol.                                 Titanate                                                                              Point °C.                                                                       wt. %    adduct  Point °C.                                                                     wt. %                                ______________________________________                                        I       dec 182  <0.5     I       73 ± 4                                                                              7                                  V       171-174  <0.5     V       <0     >25                                  AA      158-161   1       AA      12 ± 4                                                                            >25                                  AC      179-184  <0.5     AC      23 ± 3                                                                            >25                                  AE      129-134   3       AE      31 ± 3                                                                             12                                  ______________________________________                                    

This example shows the improvement in hexane solubility and meltingpoint lowering effected upon prior art phosphato titanates via thepractice of adduction as described in the present invention.

EXAMPLE 18

This example shows the utility of pyrophosphato titanate adducts asthermally activated catalysts in the controlled interconversion ofesters, i.e., the transesterification of ethyl propionate with methylbutyrate in solutions containing ethyl acetate.

In a 2 liter pyrex flask equipped with facilities for mechanicalagitation, pot and head thermometers, innert gas inlet, fractionatingcolumn (30 theoretical plates), automatic reflux-takeoff assembly,vacuum receivers, external heat and vacuum sources was placed 3 M eachof ethyl acetate, ethyl propionate and methyl butyrate, together with1.0 g of the indicated catalyst. Vacuum and reflux ratios were adjustedto 25 mm and 25:1, respectively, and the pot contents distilled torecover 97±1% of the feed overhead. Analysis of the distillate(s) wasperformed by gas liquid chromatography results are given in Table 15.

                  TABLE 15                                                        ______________________________________                                                   % Yield           %     % Re- % Re-                                           By-      % Re-    Yield covery                                                                              covery                                          product  covery   Methyl                                                                              Ethyl Methyl                               Catalyst   Methyl   Ethyl    Pro-  Pro-  Buty-                                Employed   Acetate  Acetate  pionate                                                                             pionate                                                                             rate                                 ______________________________________                                        Sulfuric                                                                      Acid       97       2        <1    95    <1                                   Aluminum                                                                      Chloride   94       5        4     97    <1                                   B          13       85       84    13    3                                    Non adducted B                                                                           89       9        8     90    3                                    H          7        91       90    8     1                                    Non adducted H                                                                           91       8        5     92    2                                    I          <1        99+     94    5     3                                    Non adducted I                                                                           87       11       10    88    2                                    J          2        96       93    5     2                                    Non adducted J                                                                           94       4        5     95    1                                    ______________________________________                                         .sup.a All numerical data in mole %.                                     

Note that both conventional acid catalysts and non-adductedpyrophosphato titanates, when employed in the above system, producesubstantial proportions of by-product methyl acetate due to preferentialvolatilization of same once formed, whereas the adducts of the instantinvention, having little catalytic activity until temperatures in excessof 50° C., permitted recovery by vacuum distillation of the bulk of theethyl acetate prior to onset of catalytic transesterification.

I claim:
 1. A composition comprising an inorganic solid and a titanatehaving the formula

    X.sub.c Ti[OP(O)(OR.sup.1)OP(O)(OR.sup.2)(OR.sup.3)].sub.4-c (NR.sup.4 R.sup.5 R.sup.6).sub.d [P(OR.sup.7)(OR.sup.8)(OR.sup.9)].sub.e

wherein c is 1 or 2; d is 0, 1 or 2; e is 0, 1 or 2; with the provisothat d plus e must be 1 or 2; with the proviso that if c is 1, X must beRO--; and with the proviso that when c is 2, X is either RO-- or a groupwhich taken together with the Ti to which it is attached forms a ringhaving the formula ##STR3## wherein each of f, g, h and i is 0 or 1,with the proviso that at least one of g, h and i is 1 and that the sumof f, g, h and i is 2 or 3; and wherein each R is independently selectedfrom C₁ to C₁₀ alkyl, C₃ to C₁₀ alkenyl, C₇ to C₁₀ dioxyalkylene; R¹,R², R⁴, R⁷, each R¹⁰ and each R¹¹ are independently selected fromhydrogen, C₆ to C₁₀ aryl, C₇ to C₂₀ aralkyl, C₁ to C₂₀ alkyl, C₃ to C₂₀alkenyl, C₂ to C₂₀ oxyalkylene and C₃ to C₂₀ oligooxyalkylene, with theproviso that one and only one of R¹ and R² is hydrogen; R⁵, R⁶, R⁸ andR⁹ are independently selected from the same groups as are R.sup. 1, R²,R⁴, R⁷, each R¹⁰ and each R¹¹, except that R⁵, R⁶, R⁸ and R⁹ may not behydrogen, and, in addition, R⁵ and R⁶ are independently selected from C₁to C₁₀ alkanol, C₂ to C₆ alkandiol, C₇ to C₁₀ aralkanol, substituted andunsubstituted C₁ to C₁₀ alkyl, substituted and unsubstituted C₃ to C₁₀aralkyl, these last four groups being optionally substituted with 1 to 3carboxylate groups or from 1 to 3 carboxamide groups, each suchcarboxylate group and each such carboxamide group being saturated orunsaturated and having from 1 to 5 carbon atoms; with the proviso thatwhen aromatic carbons are present in any one of R, R², R⁴, R⁷, R¹⁰ orR¹¹, each of said carbons is optionally substituted with 1 or 2independently selected halogen atoms.
 2. The composition of claim 1wherein the inorganic solid is a metal.
 3. The composition of claim 1wherein the inorganic solid is particulate and has a particle size ofnot greater than 1 mm.
 4. The composition of claim 1 wherein thetitanate is di(butyl,methyl) pyrophosphato ethylene titanate di(dioctylphosphite).
 5. The composition of claim 1 wherein the titanate isoxoethylene di(butyl,methoxyethyl) pyrophosphato titanatedimethoxyethylphosphite.
 6. The composition of claim 1 wherein thetitanate is 1-oxo-1,3-propylene di(bisphenyl) pyrophosphato titanatedilaurylphosphite.